Self-assembled two-dimensional arrays of either 14 nm hcp-Co or 6 nm ε-Co particle components were treated by hydrogen plasma for various exposure times. A change of hysteretic sample behavior depending on the treatment duration is reported, which can be divided in two time scales: oxygen reduction increases the particle magnetization during the first 20 min, which is followed by an alteration of the magnetic response shape. The latter depends on the respective particle species. Based on the Landau–Lifshitz equations for a discrete set of magnetic moments, we propose a model that relates the change of the hysteresis loops to a dipole-driven ordering of the magnetocrystalline easy axes within the particle plane due to the high spatial aspect ratio of the system.
dipolar particle coupling; magnetic nanoparticles; magnetocrystalline anisotropy; monolayers
The recent achievement of atomic resolution with dynamic atomic force microscopy (dAFM) [Fukuma et al., Appl. Phys. Lett.
2005, 87, 034101], where quality factors of the oscillating probe are inherently low, challenges some accepted beliefs concerning sensitivity and resolution in dAFM imaging modes. Through analysis and experiment we study the performance metrics for high-resolution imaging with dAFM in liquid media with amplitude modulation (AM), frequency modulation (FM) and drive-amplitude modulation (DAM) imaging modes. We find that while the quality factors of dAFM probes may deviate by several orders of magnitude between vacuum and liquid media, their sensitivity to tip–sample forces can be remarkable similar. Furthermore, the reduction in noncontact forces and quality factors in liquids diminishes the role of feedback control in achieving high-resolution images. The theoretical findings are supported by atomic-resolution images of mica in water acquired with AM, FM and DAM under similar operating conditions.
atomic force microscopy; dAFM; high-resolution; liquids
This review focuses and summarizes recent studies on the functionalization of carbon nanotubes oriented perpendicularly to their substrate, so-called vertically aligned carbon nanotubes (VA-CNTs). The intrinsic properties of individual nanotubes make the VA-CNTs ideal candidates for integration in a wide range of devices, and many potential applications have been envisaged. These applications can benefit from the unidirectional alignment of the nanotubes, the large surface area, the high carbon purity, the outstanding electrical conductivity, and the uniformly long length. However, practical uses of VA-CNTs are limited by their surface characteristics, which must be often modified in order to meet the specificity of each particular application. The proposed approaches are based on the chemical modifications of the surface by functionalization (grafting of functional chemical groups, decoration with metal particles or wrapping of polymers) to bring new properties or to improve the interactions between the VA-CNTs and their environment while maintaining the alignment of CNTs.
aligned; carbon nanotubes; fluorination; functionalization; graphene; nitration; oxidation
The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure–activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed.
AuAg alloy; AuCu alloy; CO oxidation; dynamic studies; kinetics; nanoporous Au (NPG) catalyst; oxygen storage capacity (OSC); temporal analysis of products (TAP)
Local curvature, or bending, of a graphene sheet is known to increase the chemical reactivity presenting an opportunity for templated chemical functionalisation. Using first-principles calculations based on density functional theory (DFT), we investigate the reaction barrier reduction for the adsorption of atomic hydrogen at linear bends in graphene. We find a significant barrier lowering (≈15%) for realistic radii of curvature (≈20 Å) and that adsorption along the linear bend leads to a stable linear kink. We compute the electronic transport properties of individual and multiple kink lines, and demonstrate how these act as efficient barriers for electron transport. In particular, two parallel kink lines form a graphene pseudo-nanoribbon structure with a semimetallic/semiconducting electronic structure closely related to the corresponding isolated ribbons; the ribbon band gap translates into a transport gap for electronic transport across the kink lines. We finally consider pseudo-ribbon-based heterostructures and propose that such structures present a novel approach for band gap engineering in nanostructured graphene.
adsorption and reactivity; curvature effects; DFT calculations; electronic transport; graphene nanoribbons; graphene nanostructuring
Four novel organotin(IV) complexes containing phosphoric triamide ligands were synthesized and characterized by multinuclear (1H, 31P, 13C) NMR, infrared, ultraviolet and fluorescence spectroscopy as well as elemental analysis. The 1H NMR spectra of complexes 1–4 proved that the Sn atoms adopt octahedral configurations. The nanoparticles of the complexes were also prepared by ultrasonication, and their SEM micrographs indicated identical spherical morphologies with particles sizes about 20–25 nm. The fluorescence spectra exhibited blue shifts for the maximum wavelength of emission upon complexation.
luminescence; nanoparticles; organotin(IV) complexes; phosphoric triamide; ultrasonic
We introduce a novel and potentially powerful, yet relatively simple extension of the spectral inversion method, which offers the possibility of carrying out 4-dimensional (4D) atomic force spectroscopy. With the extended spectral inversion method it is theoretically possible to measure the tip–sample forces as a function of the three Cartesian coordinates in the scanning volume (x, y and z) and the vertical velocity of the tip, through a single 2-dimensional (2D) surface scan. Although signal-to-noise ratio limitations can currently prevent the accurate experimental implementation of the 4D method, and the extraction of rate-dependent material properties from the force maps is a formidable challenge, the spectral inversion method is a promising approach due to its dynamic nature, robustness, relative simplicity and previous successes.
atomic force microscopy; spectral inversion; spectroscopy; torsional harmonic cantilever; viscoelasticity
Focused-electron-beam-induced deposition (FEBID) is used as a direct-write approach to decorate ultrasmall Pt nanoclusters on carbon nanotubes at selected sites in a straightforward maskless manner. The as-deposited nanostructures are studied by transmission electron microscopy (TEM) in 2D and 3D, demonstrating that the Pt nanoclusters are well-dispersed, covering the selected areas of the CNT surface completely. The ability of FEBID to graft nanoclusters on multiple sides, through an electron-transparent target within one step, is unique as a physical deposition method. Using high-resolution TEM we have shown that the CNT structure can be well preserved thanks to the low dose used in FEBID. By tuning the electron-beam parameters, the density and distribution of the nanoclusters can be controlled. The purity of as-deposited nanoclusters can be improved by low-energy electron irradiation at room temperature.
carbon nanotubes; FEBID; nanocluster; platinum; patterning; radiation-induced nanostructures; TEM
We have developed a new procedure for efficient combing of DNA on a silicon substrate, which allows reproducible deposition and alignment of DNA molecules across lithographically defined patterns. The technique involves surface modification of Si/SiO2 substrates with a hydrophobic silane by using gas-phase deposition. Thereafter, DNA molecules are aligned by dragging the droplet on the hydrophobic substrate with a pipette tip. Using this procedure, DNA molecules were stretched to an average value of 122% of their contour length. Furthermore, we demonstrated combing of ca. 900 nm long stretches of genomic DNA across nanofabricated electrodes, which was not possible by using other available combing methods. Similar results were also obtained for DNA–peptide conjugates. We suggest this method as a simple yet reliable technique for depositing and aligning DNA and DNA derivatives across nanofabricated patterns.
AFM; DNA molecular combing; DNA–peptide complexes; molecular electronics; surface modification
The influence of applied normal load and roughness on the tribological behavior between the indenter and sample surface during nanoindentation-based scratching has been experimentally investigated by using different surfaces (fused silica and diamond-like carbon) featuring various degrees of roughness. At a sufficiently low applied normal load, wherein the contact is elastic, the friction coefficient is constant. However, at increased normal loads the contact involves plastic deformation and the friction coefficient increases with increasing normal load. The critical load range for a transition from predominantly elastic to plastic contact, between the indenter and sample surface, increases with increasing size of indenter and decreases with roughness. Distinct differences between the present experimental results and the existing theoretical models/predictions are discussed.
nanoindentation; nanotribology; scratch testing; surface roughness
We investigate the excitation as well as propagation of magnetic modes in plasmonic nanostructures. Such structures are particularly suited for excitation with cylindrical vector beams. We study magneto-inductive coupling between adjacent nanostructures. We utilize high-resolution lithographic techniques for the preparation of complex nanostructures consisting of gold as well as aluminium. These structures are subsequently characterized by linear optical spectroscopy. The well characterized and designed structures are afterwards studied in depth by exciting them with radial and azimuthally polarized light and simultaneously measuring their plasmonic near-field behavior. Additionally, we attempt to model and simulate our results, a project which has, to the best of our knowledge, not been attempted so far.
near-field microscopy; oligomers; plasmons; radial and azimuthal polarization
Intermodulation atomic force microscopy (ImAFM) is a mode of dynamic atomic force microscopy that probes the nonlinear tip–surface force by measurement of the mixing of multiple modes in a frequency comb. A high-quality factor cantilever resonance and a suitable drive comb will result in tip motion described by a narrow-band frequency comb. We show, by a separation of time scales, that such motion is equivalent to rapid oscillations at the cantilever resonance with a slow amplitude and phase or frequency modulation. With this time-domain perspective, we analyze single oscillation cycles in ImAFM to extract the Fourier components of the tip–surface force that are in-phase with the tip motion (F
I) and quadrature to the motion (F
Q). Traditionally, these force components have been considered as a function of the static-probe height only. Here we show that F
I and F
Q actually depend on both static-probe height and oscillation amplitude. We demonstrate on simulated data how to reconstruct the amplitude dependence of F
I and F
Q from a single ImAFM measurement. Furthermore, we introduce ImAFM approach measurements with which we reconstruct the full amplitude and probe-height dependence of the force components F
I and F
Q, providing deeper insight into the tip–surface interaction. We demonstrate the capabilities of ImAFM approach measurements on a polystyrene polymer surface.
atomic force microscopy; AFM; frequency combs; force spectroscopy; high-quality-factor resonators; intermodulation; multifrequency
The noise of the frequency-shift signal Δf in noncontact atomic force microscopy (NC-AFM) consists of cantilever thermal noise, tip–surface-interaction noise and instrumental noise from the detection and signal processing systems. We investigate how the displacement-noise spectral density d
z at the input of the frequency demodulator propagates to the frequency-shift-noise spectral density d
f at the demodulator output in dependence of cantilever properties and settings of the signal processing electronics in the limit of a negligible tip–surface interaction and a measurement under ultrahigh-vacuum conditions. For a quantification of the noise figures, we calibrate the cantilever displacement signal and determine the transfer function of the signal-processing electronics. From the transfer function and the measured d
z, we predict d
f for specific filter settings, a given level of detection-system noise spectral density d
ds and the cantilever-thermal-noise spectral density d
th. We find an excellent agreement between the calculated and measured values for d
f. Furthermore, we demonstrate that thermal noise in d
f, defining the ultimate limit in NC-AFM signal detection, can be kept low by a proper choice of the cantilever whereby its Q-factor should be given most attention. A system with a low-noise signal detection and a suitable cantilever, operated with appropriate filter and feedback-loop settings allows room temperature NC-AFM measurements at a low thermal-noise limit with a significant bandwidth.
Cantilever; feedback loop; filter; noncontact atomic force microscopy (NC-AFM); noise
Nanostructure-decorated n-type semiconductor interfaces are studied in order to develop chemical sensing with nanostructured materials. We couple the tenets of acid/base chemistry with the majority charge carriers of an extrinsic semiconductor. Nanostructured islands are deposited in a process that does not require self-assembly in order to direct a dominant electron-transduction process that forms the basis for reversible chemical sensing in the absence of chemical-bond formation. Gaseous analyte interactions on a metal-oxide-decorated n-type porous silicon interface show a dynamic electron transduction to and from the interface depending upon the relative strength of the gas and metal oxides. The dynamic interaction of NO with TiO2, SnO2, NiO, CuxO, and AuxO (x >> 1), in order of decreasing acidity, demonstrates this effect. Interactions with the metal-oxide-decorated interface can be modified by the in situ nitridation of the oxide nanoparticles, enhancing the basicity of the decorated interface. This process changes the interaction of the interface with the analyte. The observed change to the more basic oxinitrides does not represent a simple increase in surface basicity but appears to involve a change in molecular electronic structure, which is well explained by using the recently developed IHSAB model. The optical pumping of a TiO2 and TiO2−
xNx decorated interface demonstrates a significant enhancement in the ability to sense NH3 and NO2. Comparisons to traditional metal-oxide sensors are also discussed.
chemical sensors; gas interface interactions; IHSAB theory; nitrated oxides; porous silicon
In qPlus atomic force microscopy the tip length can in principle approach the length of the cantilever. We present a detailed mathematical model of the effects this has on the dynamic properties of the qPlus sensor. The resulting, experimentally confirmed motion of the tip apex is shown to have a large lateral component, raising interesting questions for both calibration and force-spectroscopy measurements.
atomic force microscopy; force spectroscopy; lateral forces; mechanical vibrations; qPlus
In this paper we present a comparison of three different methods that can be used for estimating the stiffness of qPlus sensors. The first method is based on continuum theory of elasticity. The second (Cleveland’s method) uses the change in the eigenfrequency that is induced by the loading of small masses. Finally, the stiffness is obtained by analysis of the thermal noise spectrum. We show that all three methods give very similar results. Surprisingly, neither the gold wire nor the gluing give rise to significant changes of the stiffness in the case of our home-built sensors. Furthermore we describe a fast and cost-effective way to perform Cleveland’s method. This method is based on gluing small pieces of a tungsten wire; the mass is obtained from the volume of the wire, which is measured by optical microscopy. To facilitate detection of oscillation eigenfrequencies under ambient conditions, we designed and built a device for testing qPlus sensors.
AFM; Cleveland’s method; cross talk; force; qPlus; stiffness; STM; thermal noise; tuning fork
The electronic and structural properties of oligo- and polythiophenes that can be used as building blocks for molecular electronic devices have been studied by using periodic density functional theory calculations. We have in particular focused on the effect of substituents on the electronic structure of thiophenes. Whereas singly bonded substituents, such as methyl, amino or nitro groups, change the electronic properties of thiophene monomers and dimers, they hardly influence the band gap of polythiophene. In contrast, phenyl-substituted polythiophenes as well as vinyl-bridged polythiophene derivatives exhibit drastically modified band gaps. These effects cannot be explained by simple electron removal or addition, as calculations for charged polythiophenes demonstrate.
band gaps; conducting polymers; density functional theory calculations; molecular electronics; oligothiophenes
atomic force microscopy
We demonstrate the coupling of single color centers in diamond to plasmonic and dielectric photonic structures to realize novel nanophotonic devices. Nanometer spatial control in the creation of single color centers in diamond is achieved by implantation of nitrogen atoms through high-aspect-ratio channels in a mica mask. Enhanced broadband single-photon emission is demonstrated by coupling nitrogen–vacancy centers to plasmonic resonators, such as metallic nanoantennas. Improved photon-collection efficiency and directed emission is demonstrated by solid immersion lenses and micropillar cavities. Thereafter, the coupling of diamond nanocrystals to the guided modes of micropillar resonators is discussed along with experimental results. Finally, we present a gas-phase-doping approach to incorporate color centers based on nickel and tungsten, in situ into diamond using microwave-plasma-enhanced chemical vapor deposition. The fabrication of silicon–vacancy centers in nanodiamonds by microwave-plasma-enhanced chemical vapor deposition is discussed in addition.
CVD diamond doping; diamond; nanophotonics; NV center; plasmonic resonator; solid immersion lens
Patterning of materials at sub-10 nm dimensions is at the forefront of nanotechnology and employs techniques of various complexity, efficiency, areal scale, and cost. Colloid-based patterning is known to be capable of producing individual sub-10 nm objects. However, ordered, large-area nano-arrays, fully integrated into photonic or electronic devices have remained a challenging task. In this work, we extend the practice of colloidal lithography to producing large-area sub-10 nm point-contact arrays and demonstrate their circuit integration into spin-photo-electronic devices. The reported nanofabrication method should have broad application areas in nanotechnology as it allows ballistic-injection devices, even for metallic materials with relatively short characteristic relaxation lengths.
magnetic point contact arrays; spin laser; sub-10 nm colloidal lithography
The combination of electrodeposition and polymeric templates created by heavy-ion irradiation followed by chemical track etching provides a large variety of poly- and single-crystalline nanowires of controlled size, geometry, composition, and surface morphology. Recent results obtained by our group on the fabrication, characterization and size-dependent properties of nanowires synthesized by this technique are reviewed, including investigations on electrical resistivity, surface plasmon resonances, and thermal instability.
electrodeposition; etched ion-track membrane; finite-size effects; heavy ion irradiation; nanowire; radiation-induced nanostructures
Single- and multilayer graphene and highly ordered pyrolytic graphite (HOPG) were exposed to a pure hydrogen low-temperature plasma (LTP). Characterizations include various experimental techniques such as photoelectron spectroscopy, Raman spectroscopy and scanning probe microscopy. Our photoemission measurement shows that hydrogen LTP exposed HOPG has a diamond-like valence-band structure, which suggests double-sided hydrogenation. With the scanning tunneling microscopy technique, various atomic-scale charge-density patterns were observed, which may be associated with different C–H conformers. Hydrogen-LTP-exposed graphene on SiO2 has a Raman spectrum in which the D peak to G peak ratio is over 4, associated with hydrogenation on both sides. A very low defect density was observed in the scanning probe microscopy measurements, which enables a reverse transformation to graphene. Hydrogen-LTP-exposed HOPG possesses a high thermal stability, and therefore, this transformation requires annealing at over 1000 °C.
graphane; HOPG; hydrogenation; plasma
We report on the synthesis and magnetic characterization of ultralong (1 cm) arrays of highly ordered coaxial nanowires with nickel cores and graphene stacking shells (also known as metal-filled carbon nanotubes). Carbon-containing nickel nanowires are first grown on a nanograted surface by magnetron sputtering. Then, a post-annealing treatment favors the metal-catalyzed crystallization of carbon into stacked graphene layers rolled around the nickel cores. The observed uniaxial magnetic anisotropy field oriented along the nanowire axis is an indication that the shape anisotropy dominates the dipolar coupling between the wires. We further show that the thermal treatment induces a decrease in the coercivity of the nanowire arrays. This reflects an enhancement of the quality of the nickel nanowires after annealing attributed to a decrease of the roughness of the nickel surface and to a reduction of the defect density. This new type of graphene–ferromagnetic-metal nanowire appears to be an interesting building block for spintronic applications.
carbon; ferromagnetic; graphene; nanofabrication; nanowires; nickel; phase separation
The most important limitation for a significant increase of the areal storage density in magnetic recording is the superparamagnetic effect. Below a critical grain size of the used CoCrPt exchange-decoupled granular films the information cannot be stored for a reasonable time (typically ten years) due to thermal fluctuations arbitrary flipping of the magnetization direction. An alternative approach that may provide higher storage densities is the use of so-called percolated media, in which defect structures are imprinted in an exchange-coupled magnetic film. Such percolated magnetic films are investigated in the present work. We employ preparation routes that are based on (i) self-assembly of Au nanoparticles and (ii) homogeneous size-reduction of self-assembled polystyrene particles. On such non-close-packed nanostructures thin Fe films or Co/Pt multilayers are grown with in-plane and out-of-plane easy axis of magnetization. The impact of the particles on the magnetic switching behavior is measured by both integral magnetometry and magnetic microscopy techniques. We observe enhanced coercive fields while the switching field distribution is broadened compared to thin-film reference samples. It appears possible to tailor the magnetic domain sizes down to the width of an unperturbed domain wall in a continuous film, and moreover, we observe pinning and nucleation at or close to the imprinted defect structures.
colloidal lithography; magnetic data storage; magnetic nanostructures; percolated films